Ether acid halides and process of making them



Patented June l5, 1937 UNITED STATESA PATENT OFFICE 2,084,284 ETHER ACID HALIDES AND PROCESS F MAKIN G THEM Norman D. Scott, Niagara Falls, N. Y., assignor to E. I. du Pont de Nemours & Company, Wilmin ton, Del., a corporation of Delaware Application March 8,/ 1933, Serial No. 660,065 2z Gummi.'y (cieco-123) An object o! the present invention is to pro-y 15 vide a process tor the preparation of acid halides from organic ethers. halides and carbon monoxide. Another object of the invention is to provide a process for the preparation oi alkoxy acyl halides and the halides of polycarboxylic ether- 0 acids from the halogen substituted alkyl ethers and carbon monoxide. A still further object of the present invention is to provide a process for the preparation of methoxy acetyl chloride and diglycolic acid chloride by the interaction of chlor- 25 methyl vethers with carbon monoxide. Other objects and advantages oi' the invention will hereinaiter appear.

I have found that the halogenated aliphatic ethers and more particularly the alpha and 30 gamma substituted aliphatic ethers will react with carbon monoxide to form the alkoxy acid halides and thediacyl halides of ether-acids. The halogenated aliphatic ethers kwhich are suitable for use in the process include all such ethers which 35 do not appreciably decompose under the conditions oi' the reaction. For example, I wish to include the following halogenated aliphatic ethers and homologous ethers: the monochlormethylalkyl ethers, such for example as monochlor- 40 methyl ether, alphamonochlormethylbutyl ether; and other alphamonochloralkyl ethers, such as alphamonochlordiethyl ether, alphamonochlordipropylalkyi ethers, such as dichlormethyl ether, dichlorethyl ether, etc., corresponding beta and 45 gamma halogenated ethers `are likewise suitable,

e. g. dichlordiethyl ether, gammachlorpropylmethyl ether, gammachlorbutylmethyl ether, etc. The unsymmetrically substituted ethers as, for example. alpha, gammadichlormethyipropyi ether 50 and like ethers. may be used. The preparation ot many ci these substituted ethers is disclosed in my copending application Ser. No. 621,539. Although the above compounds are given as the chlorides of the various ethers, it is understood 55 that the other halides of these compounds may be used, for example, the bromide, iodide, and fluoride; the chloride due to its availability and ease withl which it lends itself to this reaction is, however, generally preferred.

'I'he products which are formed by the condensation of carbon monoxide with the halogenated ethers varies, of course, with the reactants and the conditions of the reaction. To illustrate an important product, the dimethyl ether-acid chloride, results from the condensation between monochlormethyl ether and carbon monoxide which may be represented by the following equation:

CH; CHI

Similarly, from carbon monoxide and.r dichlormethyl ether diglycolio acid chloride CHlCl 001C OCI omoooi f +200 QHgCl CHICOCI butyryl chloride cmomomol omomomoooi CHI 0H] Catalysts may be used, if desired, to accelerate the reaction and may include the anhydrous halides of a number' of metals such as zinc, bismuth, and antimony. I prefer to use catalysts which would be classed as easily or moderately active forthe Friedel-Craft type of reaction, in order to minimize reactions decomposing the halogenated alkyl ether. A fairly wide range o! temperatures and pressures is permissible, depending inter alla on the catalyst chosen and the type of ether being treated. Zinc chloride may be used dissolved in a chlormethyl ether and 'when used in this form it is desirable to operate at temperatures in the neighborhood'oi 50 C.' or below, and with carbon monoxide at pressures as high as is feasible, although the reaction will proceed, to a certain extent, at ordinary temperature and pressure conditions. Inert solvents may be used, if desired,4in the condensation.

The following examples further illustrate the nature o! the invention, but the invention is not restricted thereto except as it may be limited by the appended claims:

Example 1-459 grams of a 4.67% solution of zinc chloride and chlormethyl ether was placed in a sealed autoclave of 1500 cc. capacity and shaken for 8 hours at 25-50 C. in contact with carbon monoxide at a pressure of 275-625 lbs. Analysis showed the product to contain, after hydrolysis oi .the methoxy acetyl chloride to methoxy acetic acid 5% 01' the theoretical amount or that acid.

Example Z-The same mixture as that given under Example 1 was shaken in the same apparatus for seven hours at' a temperature oi' 68-86 C. and under a carbon monoxide pressure of 480-530 lbs. per square inch, the reactants were allowed to cool in the autoclave over night under the pressure of carbon monoxide. Ai'terA hydrolysis oi the methoxy acid chloride to methoiw acetic acid, a 6.2%, yield of the latter was obtained.

Example 3--201 grams of monochlormethyl ether with 10 grams oi' aluminum chloride were placed in a steel shaker bomb oi' approximately 4 00 cc. capacity. Carbon monoxide was introduced at a pressure oi' 1100 lbs. pery sq. in., the bomb was then purged to remove inert gases present. and the carbon monoxide again introduced at a pressure or 1100 lbs. Under this carbon monoxide pressure the tube was shaken i'or approximately one hour at 25 C., the temperature was then raised during a period of one hour to approximately 100 C., and the bomb shaken for eight hours. Examination of the product indicated a yield of approximately 9% methoxy acetyl chloride.

The reaction product of carbon monoxide with the halogenated ethers given is indicated in the examples as an ether-acid halide. From these acid halides a large number of organic compounds may be prepared; for example, by hydrolysis the acid is produced which may in turn 'be hydrogenated to the corresponding alcohol, by esterication the ester. by dehydration the anhydride; many other organic compounds may vbe prepared by simple reactions well known to the expert organic chemist, giving amides, ketones, etc. For example, from methoxyacetylchloride may be obtained by such known processes methoxyacetic acid, ethylene glycol monomethyl ether, esters of methoxyacetlc acid, methoxy acetic anhydride, methoxyacetamide, dimethoxy methyl ketone, etc. From the diglycolic acid chloride may be obtained the corresponding compounds, diglycolic acid, diethylene glycol, esters of diglycolic acid, diglycolic anhydride, amides (or imides) of diglycolic acid, cyclic or polymeric ketones, etc. From the acid halides prepared from the other ethers like compound may be produced. The number and variety of these compounds may be appreciated by a consideration of the single ligure, a chart in which the R and R1 designate similar or dissimilar alkyl, or aralkyl groupings; the halogen, although shown as chlorine, may likewise be bromine, fluorine,.or iodine; furthermore, the halogen need not be substituted in the alpha position as has been described, ii', of course, the R or Ri" grouping contains more than one carbon atom. Y

In my copending application U. S. Ser. No. 627,539 I have disclosed a process of reacting halogenated ethers with oleiinic hydrocarbons to produce halogenated ethers or higher molecular weight. The process therein disclosed may like- -Wise be employed for the reaction of the olelinlc hydrocarbons with the ether-acid halides, alkoxyacid halides, acid halides of the dicarboxylic oleflnic lhydrocarbon generally adding to the compounds between the carbon monoxide and halogen positions, e. g. from methoxy acetyl chloride and ethylene would be obtained methoxymethyl beta-chlorethyl ketone-from methowbutyryl chloride and ethylene-methoxy-propylbetachlorethyl ketone; from the diacid chloride o! diglycollc acid and ethylene-p5' dichlordipropionyldimethyl ether; etc.

The carbon monoxide required for the synthesis may be conveniently derived from various commercial sources, such as, for example, watergas, producerl gas, etc., by liquefactibn or other means, and should likewise, for the best results. be relatively pure, it being particularly desirable to avoid the presence therein of catalyst poisons.

'Ihe 'halogenated ethers may be prepared in any suitable manner; for example, the monochlormethyl ether is readily made from methanol.

mono-and polyhalogenated ethers are readily produced bythe chlorination of the dialkyl,v

ethers.

I claim: v

l. A process for the production of ether-acid halides which comprises reacting in the liquid phase a halogenated lower aliphatic ether with carbon monoxide at reaction temperature in the presence or a moderately active Friedel-Craft type catalyst.

2. A process for the production of alkoxy-acid halides which comprises reacting in the liquid phase a monohalogenated lower aliphatic ether with carbon monoxide at reactionl temperature in the presence of a moderately active Friedel-Craft type catalyst.

3. A process for the production o! acid halides ot dicarboxylic ether acids which comprises reacting in the liquid phase a dihalogenated lower aliphatic ether withcarbon monoxide at reaction temperature in the presence oi' a moderately active Friedel-Craft type catalyst.

4. A process for the production of ether-acid chlorides which comprises reacting in the liquid phase a chlorinated lower aliphatic ether with carbon monoxide at reaction temperature in the presence of a moderately active Friedel-Craft type catalyst.

5. A process for the production o1' alkoxy acid chlorides which comprises reacting in the-liquid phase a monochlorinated lower aliphatic ether with carbon monoxide at reaction temperature in the presence of a moderately active Friedel- Craft type catalyst.

, 6. A process lor the production or acid chlorides of dicarboxylic ether-acids which comprises reacting in the liquid phase a dichlorinated lower aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence of a moderately active Friedel-Craft type catalyst.

7. A process for the production of methoxy acetyl chloride which comprises reacting in the liquidv phase an alphamonochlormethyl ether with carbon monoxide at a temperature between 25 and 50 C. in the presence oi' a moderately active Friedel-Craft type catalyst.

8. A process for the production of an acid halide of a dicarboxylic ether-acid which comprises reacting in the liquid phase a symmetrical dialphadichlor lower alkyl ether -with carbon monoxide at a temperature between 25 and 50 C. in the presence of a moderately active Friedel- Craft type catalyst.

9. A process for the production of an alkoxy acid chloride which comprises reacting in the with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

1li. A process which comprises reacting in the liquid phase an alpha halosenated lower aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

11. A'process which comprises reactina in the liquid phase an alpha chlorinated lower aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence of a moderately active Friedel-Craft type catalyst.

12. A process which comprises reacting in the liquid phase a gamma halogenated lower aliphatic ether with carbon monoxide at a tcmperature between 25 and 50 C. in the presence of a moderately active Friedel-Craft type catalyst.

13. A process which comprises reactins in the liquid -phase a gamma chlorinated lower' aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

14. A process for the production of an etheracid halide which comprises reacting in the liquid phase a halozenated lower aliphatic ether with carbon monoxide in the presence of a metal halide catalyst at a temperature between 25 and 50 C.

15. A process for the production oi an etheracid halide which comprises reacting at a temperature between 25 and 50 C. a halogenated lower aliphatic ether with carbon monoxide in the presence of sinc chloride.

16. A process tor the production o! an etheracid halide which comprises reactinl at a temperature between 25 and 50 C. a halozenated lower aliphatic ether with carbon monoxide in the presence of aluminum chloride.

l'l. An acid halide oi a dicarboxylic ether acid.v

18. Diacid chloride of disylcoiic acid.

lil. A dibasic acid halide of dimethyl ether.

' 20. A process for the production of an etheracid chloride which comprises reacting in the liquid phase. at a temperature between 25 and 50 C., a chlorinated lower aliphatic ether with carbon monoxide in the presence ot a metal halide which is moderately active for the Friedel- Craft type of reaction and which is soluble in the chlorinated aliphatic ether as the catalyst for the reaction.

21. A process for the production o! an alkoxy acyl halide, which comprises reacting in the liquid phase, at a temperature between 25 and 50 C., an alphamonohaloaenated lower alkyl ether with carbon monoxide, in the presence of a moderately active Friedel-Craft type catalyst.

22..A process for the production of an etheracid halide which comprises reacting in the liquid phase, at a temperature between 25 and 50 C., a gamma halogenated lower alkyl ether with carbon monoxide, in the presence of a moderately active Friedel-Craft type catalyst.

NORMAN D. SCOTT.'

Certificate of Correction Patent No. 2,084,284;

June 15, 1937.

NORMAN D.. SCOTT It is hereby certified that errors appear in the printed specification ofthe above numbered patent requiring correction as follows: Page 1, second column, line 20,`

for the portion of the formule. reading CO2 read CH2; page 3, first column, line 32,

and second column, line 4, claims 15 and 16 respectively, after reacting insert tra the liquid phase; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record ,of the case in the Patent Office.

Signed and sealed this 3rd day of August, A. D.

[SEAL] HENRY VAN ARSDALE, Acting Commissioner of Patents.

with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

1li. A process which comprises reacting in the liquid phase an alpha halosenated lower aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

11. A'process which comprises reactina in the liquid phase an alpha chlorinated lower aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence of a moderately active Friedel-Craft type catalyst.

12. A process which comprises reacting in the liquid phase a gamma halogenated lower aliphatic ether with carbon monoxide at a tcmperature between 25 and 50 C. in the presence of a moderately active Friedel-Craft type catalyst.

13. A process which comprises reactins in the liquid -phase a gamma chlorinated lower' aliphatic ether with carbon monoxide at a temperature between 25 and 50 C. in the presence oi a moderately active Friedel-Craft type catalyst.

14. A process for the production of an etheracid halide which comprises reacting in the liquid phase a halozenated lower aliphatic ether with carbon monoxide in the presence of a metal halide catalyst at a temperature between 25 and 50 C.

15. A process for the production oi an etheracid halide which comprises reacting at a temperature between 25 and 50 C. a halogenated lower aliphatic ether with carbon monoxide in the presence of sinc chloride.

16. A process tor the production o! an etheracid halide which comprises reactinl at a temperature between 25 and 50 C. a halozenated lower aliphatic ether with carbon monoxide in the presence of aluminum chloride.

l'l. An acid halide oi a dicarboxylic ether acid.v

18. Diacid chloride of disylcoiic acid.

lil. A dibasic acid halide of dimethyl ether.

' 20. A process for the production of an etheracid chloride which comprises reacting in the liquid phase. at a temperature between 25 and 50 C., a chlorinated lower aliphatic ether with carbon monoxide in the presence ot a metal halide which is moderately active for the Friedel- Craft type of reaction and which is soluble in the chlorinated aliphatic ether as the catalyst for the reaction.

21. A process for the production o! an alkoxy acyl halide, which comprises reacting in the liquid phase, at a temperature between 25 and 50 C., an alphamonohaloaenated lower alkyl ether with carbon monoxide, in the presence of a moderately active Friedel-Craft type catalyst.

22..A process for the production of an etheracid halide which comprises reacting in the liquid phase, at a temperature between 25 and 50 C., a gamma halogenated lower alkyl ether with carbon monoxide, in the presence of a moderately active Friedel-Craft type catalyst.

NORMAN D. SCOTT.'

Certificate of Correction Patent No. 2,084,284;

June 15, 1937.

NORMAN D.. SCOTT It is hereby certified that errors appear in the printed specification ofthe above numbered patent requiring correction as follows: Page 1, second column, line 20,`

for the portion of the formule. reading CO2 read CH2; page 3, first column, line 32,

and second column, line 4, claims 15 and 16 respectively, after reacting insert tra the liquid phase; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record ,of the case in the Patent Office.

Signed and sealed this 3rd day of August, A. D.

[SEAL] HENRY VAN ARSDALE, Acting Commissioner of Patents. 

